Laterally dibenzyloxy-branched nematogens with large nematic range and rich solid polymorphism

Mesogenic compounds containing four rings in the core usually have very high melting points. However, when two identical lateral benzyloxy groups are introduced on the same side of one of the central rings, the melting point is lowered dramatically and a large nematic range is retained. This range is affected by the bulkiness of the para-substituents in the lateral rings. Methyl groups can be introduced in the ortho- or meta-positions with a consequent decrease in the melting temperature without much affecting the nematic range. These compounds exhibit a rich solid polymorphism which is certainly related to the effect of the conformations of the lateral substituent on the molecular arrangment in the solid phase. Some preliminary NMR experiments on the nematic phase indicate that the molecular long axis coincides with the core axis, whereas the para-axis of the lateral fragment makes an angle close to the magic angle with respect to the molecular long axis.     

Determination of the permittivity of nematic liquid crystals in the microwave region

Two 3 mm thick microscope glass plates, having one face plus their two long edges coated by a thick metallic film, are spaced 75 μm apart by mylar spacers. Because of the metallic coatings on the inner faces the structure acts as a single metallic slit. The space between the two coated plates is filled with aligned nematic liquid crystal (E7, Merck/BDH) and the cell is inserted in an absorber aperture. This single metallic slit geometry supports resonant modes when microwaves are incident with their polarization (E-field) perpendicular to the slit. The structure gives a set of Fabry-Perot-like resonant transmission frequencies. These frequencies move when a voltage is applied between the two plates, the liquid crystal being first aligned homogeneously, then realigning homeotropically with the applied field. By minotoring these changes a fast and easy to use procedure for determining the permittivity and its anisotropy for nematic liquid crystals in the microwave region has been developed. The parameters determined for E7 are ε_e = 3.17 (n_e = 1.78 ± 0.01) and ε_o = 2.72 (n_o = 1.65 ± 0.01), (Δn ≈ 0.13) in the 40.0–60.0 GHz region.     

Optical studies of dynamic director configurations in ferroelectric liquid crystal devices

An investigation into the transmission spectrum of a ferroelectric liquid crystal device is undertaken. This is done both for an initial static state and during a switching process. Comparisons are made between experimental data and theoretical predictions. The dynamic internal director configurations in the device is shown to be consistent with a simple model during both monopolar and bipolar addressing pulses.     

Study of the electrocaloric effect in ferroelectric liquid crystals

ABSTRACT

Electrocaloric effect (ECE) in two ferroelectric liquid crystalline (FLC) materials has been evaluated by mean of two indirect characterization methods: the photopyroelectric (PPE) technique and the polarization current reversal one. The obtained results show a good correspondence of the adiabatic temperature change associated with the ECE evaluated from both methods. This validates the possibility to use the PPE technique to investigate the ECE in FLCs. This study also demonstrates that FLCs can be used as electrocaloric material. More particularly, it shows that as for their solid homologous, liquid crystals displays more pronounced ECE in the vicinity of a first order transition than that measured near to second-order one.     

Finite Element Based Micro-mechanical Modeling of Interphase in Filler Reinforced Elastomers

Characteristic properties of elastomers can be tailored by embedding them with filler particles. Along with enhancing the overall properties of the composite, filler particles also induce some inelastic effects. In this paper, a finite element computational model is used to study the effect of microstructure morphology in filled elastomers, on its macroscopic large deformation behavior. A multiphase material model that accounts for the hypothesis of shift in glass transition temperature in the vicinity of the filler particle is developed to simulate the interphase between the fillers and the matrix. It also accounts for the breakdown and re-aggregation of filler networks under cyclic loading. Examples at the microstructural level, demonstrating the dynamics of the interphase using the developed multiphase model have been successfully simulated. The obtained results are in good qualitative agreement with the Mullins effect. Therefore, computational experiments using this methodology enable the prediction of the experimentally observed softening behavior in filled elastomers based on its microstructure evolution.     

Oxidation of aliphatic alcohols by triethylammonium chlorochromate in non-aqueous medium – A kinetic and mechanistic study

The oxidation of some aliphatic alcohols by triethylammonium chlorochromate (TriEACC) in dimethyl sulfoxide leads to the formation of the corresponding carbonyl compounds. The reaction is first order with respect to TriEACC. The reaction exhibited Michaelis–Menten type kinetics with respect to alcohol. The reaction is catalyzed by hydrogen ions. The hydrogen-ion dependence has the form: k_obs = a + b[H⁺]. The oxidation of [1,1-²H₂] ethanol (MeCD₂OH) exhibits a substantial primary kinetic isotope effect. Oxidation of aliphatic alcohol was studied in 19 different organic solvents. The solvent effect has been analysed using Kamlet’s and Swain’s multi-parametric equation. A suitable mechanism has been proposed.     

Investigation of chemical activity,SCHIFF base reactions and staining effects of some amino acids by spectrophotometric and theorical methods

In this study, the staining properties of selected amino acids with Brassica oleraceae extract in alum and alum-free media were investigated. Basic, acidic and neutral amino acids (arginine, glutamic acid and glycine) were used to investigate the effect of staining. It was determined that all amino acids were stained in alum media. In the second step, the R group of amino acids found in the proteins of the cell nucleus was reacted with salicyl aldehyde. This reaction was successful only with Arginine. The staining properties of the newly formed compound were also investigated in alum and alum-free environments. Evaluation of the results was done using FT-IR and ¹H NMR methods. All compounds were optimized with the Gaussian G09 program (DFT/B3LYP/6.311 ?G(d.p) basic set. HOMO, LUMO and HOMO-LUMO gap values were determined. Chemical reaction capabilities of amino acids were discussed with the help of HOMO-LUMO gap values.     

Degradation of 4-chloro 2-aminophenol using combined strategies based on ultrasound,photolysis and ozone

The present work investigates the degradation of 4-chloro 2-aminophenol (4C2AP), a highly toxic organic compound, using ultrasonic reactors and combination of ultrasound with photolysis and ozonation for the first time. Two types of ultrasonic reactors viz. ultrasonic horn and ultrasonic bath operating at frequency of 20 kHz and 36 kHz respectively have been used in the work. The effect of initial pH, temperature and power dissipation of the ultrasonic horn on the degradation rate has been investigated. The established optimum parameters of initial pH as 6 (natural pH of the aqueous solution) and temperature as 30 ± 2 °C were then used in the degradation studies using the combined approaches. Kinetic study revealed that degradation of 4C2AP followed first order kinetics for all the treatment approaches investigated in the present work. It has been established that US + UV + O₃ combined process was the most promising method giving maximum degradation of 4C2AP in both ultrasonic horn (complete removal) and bath (89.9%) with synergistic index as 1.98 and 1.29 respectively. The cavitational yield of ultrasonic bath was found to be eighteen times higher as compared to ultrasonic horn implying that configurations with higher overall areas of transducers would be better selection for large scale treatment. Overall, the work has clearly demonstrated that combined approaches could synergistically remove the toxic pollutant (4C2AP).     

Organozinc Pivalate Reagents: Segregation,Solubility, Stabilization,and Structural Insights

The pivalates RZnOPiv?Mg(OPiv)X?n LiCl (OPiv=pivalate; R=aryl; X=Cl, Br, I) stand out amongst salt‐supported organometallic reagents, because apart from their effectiveness in Negishi cross‐coupling reactions, they show more resistance to attack by moist air than conventional organometallic compounds. Herein a combination of synthesis, coupling applications, X‐ray crystallographic studies, NMR (including DOSY) studies, and ESI mass spectrometric studies provide details of these pivalate reagents in their own right. A p‐tolyl case system shows that in [D₈]THF solution these reagents exist as separated Me(p‐C₆H₄)ZnCl and Mg(OPiv)₂ species. Air exposure tests and X‐ray crystallographic studies indicate that Mg(OPiv)₂ enhances the air stability of aryl zinc species by sequestering H₂O contaminants. Coupling reactions of Me(p‐C₆H₄)ZnX (where X=different salts) with 4‐bromoanisole highlight the importance of the presence of Mg(OPiv)₂. Insight into the role of LiCl in these multicomponent mixtures is provided by the molecular structure of [(THF)₂Li₂(Cl)₂(OPiv)₂Zn].